The development of efficient synthetic methodologies and post-functionalization procedures gave access to a wide variety of new corrole derivatives with potential applications in different areas. This paper reviews the preparation of meso-triaarylcorroles and their functionalization, namely via cycloaddition transformations, and describes the nonlinear optical (NLO) properties of a series of metal-free and gallium corroles with different peripheral substituents. The corroles studied were the free base 5,10,15-tris-(pentafluorophenyl)corrole, the corresponding gallium(III) complex and adducts obtained from 1,3-dipolar cycloaddition reaction. Correlations between the structure and the NLO effect of optical power limiting were attempted in our...